Process for the production of polymerization products



Patented Nov. 16, 1 943 PROCESS FOR THE PRODUCTION OF POLY- MERIZATIONPRODUCTS Heinrich Hope and Siebert Goebel, Ludwigshafen-on-the-Rhine,Germany, assignors, by mesne assignments, to General Aniline & FilmCorporation, New York, N. Y., a corporation of Delaware No Drawing.Application March 6, No. 322,547. In Germany March Claims.

The present irfvention relates to a process for the production ofpolymerization products.

The copending application Ser. No. 309,238, filed December 14, 1939, bythe present inventors and Curt W. Rautentrauch, describes a process forthe production of polymerization products in which ethylene, ff desiredin admixture with other polymerizable compounds, is subjected topolymerization in an aqueous emulsion in the presence of substancessupplying oxygen,

We have now found that ethylene may be converted into solid orsemi-solid polymerization products in a very simple manner by efiectingits polymerization in the presence of organic solvents and oxygen orsubstances supplying oxygen. The organic solvents may be used eitheralone or'in combination with aqueous liquids in which the solvents andthe ethylene are emulsifled or dissolved. By our new method of workingthe solid polymerization products may be ob tained under relatively lowsuperatmospheric pressures. comparatively small proportions of organicsolvents, say from 10 to 100 per cent (percentage by weight withreference to ethylene) are suflicient for obtaining good yields of solidpolymerization products at between about 100 and about 300 atmospheres,whereas considerably higher pressures are required when conducting theprocess in the absence of organic solvents.

Among the substances having an accelerating efiect in the polymerizationwe may mention oxygen or substances supplying oxygen, especiallyperoxidic substances, for example persulphates, percarbonates,perborates as well as benzoyl= peroxide, peracetic acid,diacetylperoxide, toluic acid peroxide and oleic peroxide which areobtainable from the acid chlorides by means of hydrogen peroxide-andcaustic soda solution.

As suitable organic solvents we may mention by way of example benzene,toluene, xylene and halogenated hydrocarbons, such as ethylene chloride,carbon tetrachloride and chlorbenzene.

Interpolymerization products may be produced by treating ethylenetogether with further unsaturated substances which in their turn arecapable of polymerization under the conditions employed, i, e.substances capable of polymerizing alone under the conditions concernedand substances which polymerize only when exposed to the polymerizingconditions in conjunction with substances polymerizable by themselves.Among substances polymerizable by themselves we may mention by way ofexample propylene, isobutylene, butadiene, styrene and acrylic acidesters;

compounds not polymerizable by themselves but 1940, Serial 14, 1939 inconjunction with polymerizable substances are for example maleic aciddiethyl ester and dimethyl ester. By varying the proportions of thecomponents employed, the properties of the polymerization products maybe varied considerably.

The polymerization products are suitable for a great variety ofapplications. They may be worked as plastics by injection-moulding orused for coating electrical conductors or for the manufacture ofcondensers. When dissolved in organic solvents they may be used for thepreparation of coatings resistant to acids and alkalies.

The following examples serve to illustrate how our present invention maybe carried out in practice, but the invention is not restricted to thesaid examples. The parts are by weight.

Example 1 100 parts of liquid ethylene, 100 parts of benzene and 2 partsof benzoyl peroxide are heated ina pressure vessel at from to C. After ashorttime the initial pressure of 100 atmospheres falls to about 70atmospheres. After removing any unpolymerized ethylene and distillingofi the solvent, the polymerization product is left behind in the formof a white waxy mass melting above 100 which may be purified byredissolving from organic solvents. 1

When using toluene instead of benzene a valuable polymerization productis likewise obtained. If trichlorethylene is employed instead of henzenean interpolymerization product containing chlorine is obtained havingsimilar properties.

Example 2 Example 3 100 parts of ethylene, 200 parts of methanol and 2parts of benzoylperoxide are mixedin a pressure resisting vesselprovided with a stirring device and heated to from to C. for 2 hours.The pressure, being 80 atmospheres at the outset, rises to atmospheresand falls Example 4 100 parts of ethylene, 150 parts of water, 50

parts of butanol and-2 parts of benzoyl peroxide are heated at from 100to 110 C. in a pressure vessel for 4 hours while stirring. A suspensionof polyethylene in butanol is thus obtained. By filtering by suction anddrying finely pulverized polyethylene is obtained which melts at between100 and 103 C.

Example 5 100 parts of ethylene, 200 parts of methanol and 3 parts ofhydrogen peroxide are heated at from 90 to 100 C. in a pressure vesselfor 6 hours while stirring. A finely pulverized polyethylene isobtained.

Example 6 100 partsof ethylene, 100 partsof methanol, 100 parts of waterand 3 parts of potassium persulphate are heated at from 120 to 130 C. ina pressure vessel for 5 hours while stirring. Besides high-melting solidpolyethylene there are obtained semi-solid polymerization products whichmelt at between about 60 and 80 C.

Example 7 100 parts of ethylene, 150 parts of methanol and 1 part ofoxygen are heated in a pressuretight vessel at from 1'70 to 180 C. forhours. A finely pulverized polyethylene is thus obtained which meltsbetween 102 and 107 C.

Example 8 100 parts of ethylene, 80 parts of benzene, 10 parts ofdichlorethylene and 4 parts of oleic peroxide are heated in the courseof 3 hours up to 85 to 95 C. in a pressure vessel provided with astirring device; stirring is continued for 5 hours at the sametemperature. By working up in a manner analogous to that described inExample 3 a fine powder is obtained from which foils may be readilyobtained by rolling.

Example 9 100 parts of ethylene, 80 parts of methanol, 10 parts ofisobutylene and 4 parts of benzoyl peroxide are heated together in apressure vessel provided with a stirring device; heating up to 95 to 100C. is effected in the course of 3 hours and stirring is continued foranother 10 hours at the same temperature. By working up as described inExample 3 a solid interpolymerisate is obtained which contains some oilyconstituents.

Example 10 100 parts of ethylene, parts of methanol. 25 parts of styreneand 2 parts of benzoyl peroxide are heated in the course of 8 hours upto C. in a pressure vessel provided with a stirring device; stirring iscontinued for 2 hours at this temperature. The reaction mixture is thenheated in the course of 3 hours up to C. at which temperature stirringis continued for another 2 hours. By working up as described in Example3, an interpolymerisate is obtained containing 20 per cent ofpolystryrene; foils may be readily obtained therefrom according to knownmethods.

Example 11 100 parts of ethylene, 150 parts of methanol,

25 parts of' acrylic acid ethyl ester and 6 parts of hydrogen peroxideare heated together up to 55 to65 C. in the course of 6 hours in apressure vessel provided with a stirring device; stirring is continuedfor 8 hours at this temperature. The reaction product which is obtainedafter working up is a thermoplastic material containing 10 per cent ofethylene in interpolymerized form.

What we claim is:

1. A process for the production of from semisolid to solidpolymerization products which consists in subjectingethylene inadmixture with a further unsaturated compound, capable of copolymerizingwith ethylene under the reaction conditions, the unsaturation of saidcompound being attributable to double bonds, to copolymerization in theliquid phase at a temperature of about 55 to C. and a pressure of about100 to 300 atmospheres in the presence of an inert organic solvent andas a polymerization catalyst a substance selected from the classconsisting of oxygen and substances supplying oxygen under the reactionconditions.

2. The process for the production of from semi-solid to solidpolymerization products from ethylene which comprises subjectingethylene in the liquid phase to a temperature of about 55 to 180 C.under a pressure of about 100 to 300 atmospheres in the presence of aninert organic solvent and as a polymerization catalyst a substanceselected irom the class consisting of oxygen and substances supplyingoxygen under the reaction conditions.

3. The process as defined in claim 2 wherein the polymerization catalystis a peroxide.

4. The process as defined in claim 2 wherein the inert solvent is abenzene hydrocarbon.

5. The process as defined in claim 2 wherein the inert solvent is achlorinated aliphatic hydrocarbon containing not more than two carbonatoms.

HEINRICH HOPFF. SIEBERT GOEBEL.

